Organic alkaline earth metal complexes and method of making same



Patented Nov. 4, 1952 ORGANIC- ALKALINE EARTH METAL COM-1 PLEXES. AND METHOD OF -MAKING SAME- Peter A. Asseff, Thomas W. Mastin, and Alan Rhodes, Cleveland, Ohio, assignors to The ration of Ohio Lubriz ol Corporation, Wickliffe, Ohio, a corpo- No Drawing. Application March 28, 1952, Serial No. 279,258

sol i (01.260-399) This application is a, continuation-in-part of Ser. No. 263,963, filed December 28, 1951, which in turn was a division of Ser. No. 216,103, and

is related to co-pending applications: Ser- No. 216,101, filed March 16, 1951; Ser. No. 216,102, filed March 16, 1951; Ser. No. 224,458, filed May 3, 1951; Ser. No. 263,961, filed December 28, 1951; Ser. No. 263,962, filed December 28, 1951; and Ser.'No. 276,462, filed March 13, 1952.

This invention relates to organic metal complexes and novel methodsfor the production of such complexes.

It is now well known that when preparing a salt or soap of an organic acid, the mere use of an excess of neutralizing agent, whichin-the priorart has been in the form of the oxide, hydroxide, carbonate, etc. of the desired metal,

may result in a product which contains an amount of metal in excess of that theoretically required-to replace the acidic hydrogens of the,

organic acid used as the starting material.

Work with this type of product has shown that for many uses, particularly where extreme care must be exercised to prevent the composition from being corrosive, as for example in lubricants, desirable resultsare secured by the use of these so-called basic salts or soaps.

Among the earlier workers in the art who recognized this factor and indicated that the use of basic soaps was desirable was Bergstrom who, in his Patents Nos. 2,270,577 and 2,279,086, made reference to the desirability of using the basic soap without, however, giving any specific method for the preparation of such soaps. A similar disclosure is found in Van Ess Patent No. 2,372,411. V V

With the demonstrated superiority of such basic soapsover the normal or slightly acidic soaps, the prior art workers then attempted to find ways of increasing the basicity of the soaps, or statedin another way, increasing the amount of metal, for example, heldin stable form in what was termed as' a' metal complex; One of the earliest patents referring to thesebasic salts as complexes or coordination compounds is McNab No. 2,418,894, who gives no indication in his patent as'to the ,molecular'structure of the product. As mi ht be expected, one of the first steps employed to produce a metal salt having an intended large excess of metal in combination was to use an? unusually large excess of Lheutralizing. agent, such fa s, lime. A representative stemnsgnsmg this procedure is Griesingen et 1" No 2 402'325who suggested the use 'of neutral zing agent up. to 220 93131 ,Tthe theo- 45.- will hereinafter be referred tq as the metal retical amount. This large excess of neutralizing agent'was employed in 'a process more or less conventional for producing salts or soaps ex cepting that the process was carried out in the presence of steam inorder to facilitate the formation' of the product.

"Thework of Gries'in'ger was followed by the work of Campbell "andljellin'ger as given in Patent No. 2,485,861. These patentees base their disclosure on the hypothesis that minor amounts ofian alkaline earth metalhydroxide or carbonate canbe'p'eptized," or'h'eld'in astate of colloidal suspension in oil by means of an oil-soluble mahogany sulphonate. Another worker in the, artwho'sought to combine in such complexes an excess amount of metal was Mertes whose Patent No. 2,501,731 was granted March 28, 1950. Mertes first prepared the normal soap and stated that such soap or soap concentrate may have additional base combined therewith by a more or less simple mixing and heating operation followed by filtering, The disclosure in Mertes appearsto indicate that his product is similar to that of Campbell and Dellinger, in that the excess neutralizing agent was held in the product suspe 'i sionby means of these prior art processes. The greatest total amount of alkaline earth metal'whi'ch can possibly be thus incorporated in the product by means of any of these prior art processes has been obtained when using barium and infthat case it is, equal to about 2.3 times the theoretical amount present in the normal salt. For the purpose of the present invention the ratio of the total metal in complex to the mquht' of me'tal which is in the form of,

the normal salt of, the oil soluble organic acid ratio.

By means of the. present invention, it is now 9 .5 9 o. b ain k i eleer hf e al e complexes which contain moremetal or higher metal ratios than is possibly' by prior art processes With re ard to lubr an s, these high metal -pl i ie ltelerle eser r. exam ta?- ti 1 ed as det ntS, 2 3d by reason of the, metal concentration can be, used in amounts appreciably less than other additives known in the prior art in order to attain a desired level of performance. It will also be observed that by virtue of the more effective nature of the present complexes in lubricants, usually it will cost less to obtain a desired result, because appreciably less additive is required. The alkaline It is a principal object of our invention to provide an alkaline earth metal organic complex which contains in stable form an amount of metal substantially greater than that contained in any of the so-called alkaline earth metal complexes previously produced. It'has been found that a metal ratio substantially greater than that possible with the prior art processes give results which are strikingly superior, especially in the field of lubricants in which these products have particular utility.

It is a further object of this invention to produce by our improved process, complexes which, while containing the same amount of alkaline earth metal as in complexes produced by the prior art process above described, are nevertheless difierent from and superior to such prior art complexes.

Still another object of this invention is to provide novel methods of producing organic alkaline earth metal complexes.

Further objects of our invention will appear as the description proceeds.

' To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

In its broadest aspects, the process of the present invention comprises combining a saltforming material with an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) in the presence of a material which is referred to hereinafter as the promotor. The precise function of the promotor material is not specifically understood since it has not been possible to specifically identify the molecular structure of the product produced. At present, it appears that none of the complexes, i. e., either those prepared by prior art techniques or those obtained under the present invention are susceptible of precise identification. This is clearly shown with respect to the prior art com-.

taining complexes are actually colloidal suspen-' sions or dispersions in which the salt of the organic acid is the peptizing agent. In the present invention, the immediate product is produced by the use of a promotor, and at least one stage contains the promotor in chemical combination. It is possible, however, to recover the promotor from the product by suitable treatment as hereinafter explained, and the final product which then has a constitution different from the initial end product is, similar to the initial product, of utility as a lubricant additive.

Stated more particularly, the present invention comprises the improvement in the process of producing an alkaline earth metal complex of oil-soluble organic acids, wherein an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) is caused to combine with a saltforming metal compound under conditions which would produce a normal salt, which comprises increasing the amount of metal which will be thus combined by having present in the process mass.

} (a) An amount of such metal compound substantially in excess of the stoichiometric amount required to form the normal metal salt;

(b) An enolic organic compound selected from the class consisting of those enolic organic compounds which are water-soluble at a temperature of 50 C. to the extent of at least 0.0005% and which in the presence of water an ionization constant greater than about 1 l0- at about 25 C.; and the salts of such organic compounds; and

(0) Water, including free and combined water in the other components;

and maintaining the mass at a temperature and for a period of time sufiicient to drive off substantially all free water and water of hydration which may be present.

A more specific aspect of the process comprising this invention may be defined as the process of producing an alkaline earth metal organic complex which comprises:

I. Preparing and mixing a mass in which, at 50 C., at least 50% of the components are in the liquid state and which mass the active components consist of A. An oil soluble organic acid compound; B. An enolic organic compound having:

(1) An ionization constant in water of at least about l 10 at about 25 C.; (2) A water solubility at 50 C. of at least about 0.0005%; and (3) In saturated aqueous solutions at about 25 C. a pH of not greater than about '7; the relative amounts of A and B used being in the range of from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B;

C. An inorganic alkaline earth metal compound (1) Which is water-soluble at a temperature of 50 C. of at least 0.0003% (2) In an amount such that there are present in the mass substantially more than 1 equivalent of alkaline earth metal, including the alkaline earth present in the remaining components, per equivalent of A plus B; and D. Water, in an amount equal to at least about one mole per mole of Ca,

51 II. And then maintainingzthe; mass at a temperature andfor aperiod .of time sufiicient to drive off substantiallyall free waterand water of hydration which may be present.

In the above-outlined processes, following Step II, the mass or product can be optionally treated in accordance with'Steps III and IV given below.

IIL'Then treating the mass or product with a material which inthepresenceof the mass or product will forma material having 'ahigher' ionization constant than the promoter, and optionally; IV. Removing from the mass or product so much of the liberated or'released' promoter asmay have been formed by Step'III.

The following examples give the preparationofa: plurality of products whichran-ge i-nmetalcon:

tent from about that of the normal-salt up to many times that amount.

We have found that sulphateash and/or metal contentvalues, and the metal ratio :values calculated therefrom, are one means for characterizing certain of the saltrcomplexes. As the description of the invention proceeds, it will become apparent that the neutralization number of a salt complex is in certain instances an unreliable index of the amount of excess metal in such complex, since it is greatly affected by the type-of" substantially neutral character, whereas in other instances a salt complex of high alkalinity has has been found to produce the desired results. The present invention contemplates the use of a promoter, in thiscase an .enoliccompound,v

in the preparation. of organic metal complexes. A pair of experiments was conducted using conventional. techniques, without a promoter, at twodifferent temperatures, 150 C. and'200'C. It will be observed from these. two. experiments, Examples 1 and 2.below, that temperature has littleor no effect onthe amount of metal which can be incorporated into the complex.

EXAMPLE 1 2500-gramsof a 30%. oil solution of barium petroleum sulphonate containing 7.6% -sulphate ash were heated to 95 C. and a slurry of barium oxide containing 386 grams ofv barium oxide and 1215 grams of water" was" added thereto. The mixture was stirred for one hour at a temperature of 100 C. and then heatedslowly over a period of three hours to a. temperature .of 150 C. This temperature was maintained for about one hour until substantially all the water was re.- moved; The salt complex thus produced had thefollowing properties:

Basic No -4 38.4

Percent sulphate ash 1610 Metal ratio" 2.25"

EXAMPLE'Z'.

In this example the procedure employed in:.Ex-

ample 1 was followed except that the dehydration step was conducted at a temperaturepfuZOO-s ta-inedhad the-.followin propertiesi BasicNownn 29.0 Per-centisulphateash- -1. 15.8 Metal ratio 2.16

From-,theabove Examplesl and2 it can be. seen that- ,salt, .complexes obtainedby conventional techniques will only have metal ratios as. high as 2.25 or approximately 2.3, regardless of the temperatures "employed; By comparison, the process of the'present invention will in every instance, wherein a substantial amount of excess inorganiczalkalineearth metal compound is employed,:,and;when using anenolicvcompound as a. promoten; produce products containing more. metal than. is :possible by any of the prior art- The following examples: illustrate:

techniques. the present invention. employing an enolic compound as promoter.

EXAMPLEB 630 grams of a 30% oil solution of barium petroleum sulphonate (7.6%sulphate ash) were admixed with'350 grams of nitro-paratfin wax (ratio of equivalents is 0.59). Then 760 cc. of water was added, followed by the addition of 296 grams of BaO; For one hour the mixture was agi tated' at -100 C., whereupon the temperature was raised to 150 C. and held at that level for one hour... Themixture was. filtered,.and the complex obtainedhad. the following properties:

EXAMPLE 4 2050' grams of a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 73.5 grams of l-nitro-propane (ratio of equivalents is 1.62) and heated to a temperature'of C. 388 grams of barium oxide and 1035 ml. of water were added to the mixture and the temperature was maintained for a period of one hour at C. Thereafter the temperatureof the mixture was slowly raised to 150 C. over a period of 2% hours and maintained at that level for a period of one hour. The product was an oily liquid, reddish-brown in color, and contained a slight odor. were determined for the product;

Basic-No; 78.2

Per cent sulphate ash v 28.2

Metal ratio .,4.60

EXAMPLE 5 grams 0f BaO over a one hour period. The en-- tire mixturewas held at 94 C. for one hour, followedby-aone hour period of heating at 150 C.

Prior to filtering, the mass was blown with CO2 forone hour-at -150 C. The filtered prodnot analyzed as follows Acid No. 0.2 Percent sulphate ash 22.8 Metal ratio 3.48.

EXAMPLE; 6

1,120 grams of a 45% oil solution of calcium.

pe r leum sulphonate, havi g a;su phateashc n tent of. 6.5%.... 9. grams of l-nitror-pr p n The following properties (ratio of equivalents is 1.52), 150 grams of- Ca(OH)z and 830 ml. of water were mixed together, and heated to about 100 C. for about one hour. The temperature was then raised to 150 C. and held at that level for one hour. The product was separated by filtering, and was found to be a viscous liquid, brown in color, and contained a faint odor. The product possessed the following properties:

Basic No 36.1 Percent sulphate ash 13.15 Metal ratio 2.36

For the purpose of comparison, calcium petroleum sulphonate was overbased with Ca(OH)2 in accordance with a conventional technique, without using a promoter, and is illustrated in Example 7 below.

EXAMPLE 7 Basic No 7.90

Percent sulphate ash 5.15

Metal ratio 1.29

EXAMPLE 8 1071 grams of a 30% oil solution of barium petroleum sulphonate (7.6% sulphate ash content), 100 grams of l-(p-nitrophenyl)-2-nitrobutane (ratio of equivalents of sulphonate to promoter is 1.7), and 506 grams of water were stirred together at 80 C. and 190 grams of BaO were added. The whole was heated for 1 hour at 100 C. and then the temperature was raised to 150 C., whereupon CO2 was blown into the mass until a substantially neutral titre was obtained (about minutes required). The mass was then filtered to yield the desired metal complex (the filtrate), which was a brown, free-flowing, oilsoluble liquid having the following analysis:

Basic No 0.22

Percent sulphate ash 20.4

Metal ratio 3.34 EXAMPLE 9 555 grams of a 40% oil solution of barium petroleum sulphonate (10% sulphate ash content), 52 grams of gamma-nitro methyl hexoate (ratio of equivalents of sulphonate to promoter is 1.7), 500 grams of low-viscosity, solvent-extracted Mid-Continent oil, and 70 grams of water were stirred at 70 C. and 135.5 grams of BaO were added. The whole was heated for about 1 hour at 100-110 C. Then the temperature was raised to 150 C., where it was held for the following operations: one hour for rough drying, 0.5 hour for CO2 blowing until a substantially neutral titre was observed, and 0.5 hour for the removal of any water present. The mass was mixed with 60 grams of nonyl alcohol and filtered to yield the desired metal complex (the filtrate), which was a brown, free-flowing, oil-soluble liquid having the following analysis:

Acid No 0.5 Percent sulphate ash .r.. 16.3 Metal ratio 3.44

8 EXAMPLE 10 555 grams of a 40% oil solution of barium petroleum sulphonate (10% sulphate ash content), 36 grams of l-chloro-l-nitro-propane (ratio of equivalents of sulphonate to promoter is 1.7), 102 grams of a low-viscosity, solvent-extracted Mid-Continent oil, and 70 grams of water were stirred at 70 C. and 135.5 grams of BaO were added. The whole was heated for one hour at -110 C. Thereafter the temperature was increased to 150 C., where it was held for the following operations: one hour for rough drying, 0.5 hour for CO2 blowing until a substantially neutral titre was obtained, and an additional hour to remove substantially all of any remaining water. The metal complex was isolated by filtration and was found to be a moderately viscous, brown, oil-soluble liquid having the following analysis:

Basic No 2.0 Percent sulphate ash 26.0 Metal ratio 3.7

EXAMPLE 11 Basic No 3.0 Percent sulphate ash 20.7 Metal ratio 3.7

EXAMPLE 12 grams of a 40% oil solution of barium petroleum sulphonate (10% sulphate ash content), 90 grams of isophorone oxime (ratio of equivalents of sulphonate to promoter is 1.7) and grams of water were stirred at 70 C. and 271 grams of BaO were added. The process was then continued in the manner set forth in Example 10. Filtration of the process mass yielded the desired metal complex, which was a free-flowing, brown, oil-soluble liquid having the following analysis:

Basic No 6.0 Percent sulphate ash 32.8 Metal ratio 4.31

EXAMPLE 13 550 grams of a 40% oil solution of barium petroleum sulphonate (10% sulphate ash content), 29.2 grams of 4-keto-2-penty1idene imine (ratio of equivalents of sulphonate to promoter is 1.7), 200 grams of a low-Viscosity, solvent-extracted Mid-Continent oil, and 70 grams of water were stirred together at 70 C. and 135.5 grams of BaO were added. The process was then continued in the same manner set forth in Example 10. The metal complex was isolated by filtration and was a free-flowing, brown, oil-soluble liquid having the following analysis:

Basic No 2.0 Percent sulphate ash 20.5 ratiO 3'1 low'viscosity,

aerate 555 grams ofa 40% oilsolution of bariumpe- 'troleumsulphonate (10 sulphate ash content) '36 grams of N-bu-tyl 'benzamide (ratio of equivalents' of sulphonate to promoter is 1 ;7) 100 grams of a low-viscosity, solvent-extracted-Mid Continent oil; and 70 grams of water were stirred together at 70'C.-and 135-.5grams of-BaO-were added. "The process was-then-continued"in the same manner set forth in Example 10. Filtration was a free-flowing, brown, oil-solubleliquid having the'following analysis:

Basic No -.-.4-..3

Percent sulphate-ash 21.4

Metal .ratio 2.88

' 555 grams..of, a.,.40% 'oilso1ution of-barium pe troleum sulphonate (10% sulphate ash content), 46 grams of o-chlorobenzamide (ratio of equivalents of sulphonate to promoter is 1.7), 100 grams of a low-viscosity;solvent-extracted Mid- Continent oil, and 65 grams of water were stirred together at 70 C. and 135.5 grams of BaO were added. The process .was then continued in the same manner set forthin-Example 10. The metal complex. was isolated by-:filtrationand was a free-flowing; brow-n, oil-soluble liquid (having; the

following analysis Acid- N 20.5

Per cent sulphate ash 29.2

"Metal "ratio 4.32

EXAMPLE 16 7 555 grams of a .40-%i oil solution'of Jbari-um =peztnoleumisulphonate 10% sulphate ashcontent) 35.8 :gramssof benzamide (ratio; of equivalents of sulphonate to promoter: is 1.7),rand sfio gramswf water were stirredxtogether at 70? C. .and 135.5

gramsofiBaO were added. The process was then continued in thesamemannenset forth in:Ex-

ample-10. Filtrationof the process-mass yielded the :desired 2 metal complex, ---which 1 was a moderately viscous brown, oil-'-soluble 'liquid having the 'followingqanalysis BasicNo 113.0

Per cent sulphate .ash "i28.2

Metal ratio -3 3147 EXAMPLE. 17

1110 grams of a40% oil solution of barium petroleum' sulphonate ('10 sulphate ash content) 79.5 grams "of acetanilide (ratio "of equivalents'of sulphonate to promoter is 1.7 271.grams 'ofBaO, and 111 grams of waterwere stirred together for one hour"a't.100'l05C. "Thereafter the temperature'was raised to 150 'C.,. and'COz waslblown through the mass for 2 hours at 11"50-1'80C. .Filtratiomyielded' the metal complex, Which was 'a' brown, *oil=soluble liquid having the "following analysis:

.AcidNo 0.3 Pertcent'sulphate ash 29.6 Metal 1 ratio 3.69

555 grams of a 40% oil solution of barium. petroleum sulphonate sulphate ash content), 17.4 gramsbf acetamidelratio of equivalents of sulphonate to promoter is 1.7), loorgramsof a solvent-extracted 'Mid Continent oil, "and '58 grams "of water'were stirred together 1-0 added. iThe-Whole washeated -for-1' hourat ;100-110 C. and l-hour at about 150;C.j Thereafter CO2 was blown into the-mass at "150 C.

until a substantially neutraltitre was Obtained (about 0.5 hour required). Added 15 grams of nonyl alcohol to the process mass and filtered to separate the desired metal complex (the filtrate) which was a moderately viscous-brown, oil-soluble liquid having the following anaysis:

Basic No 3.7 Per cent suphate ash 21.2 ,Meta1:ratio. 2.77

555grams of a 40% oilysolution of hariumzPetroleum sulphonate 10%, sulphate ashcontent) .38 grams of ethyl ,acetoacetate (ratio of equivalents of sulphonate to .hrczmoteris 1.7),andg60 grams of water were stirred "together... at- =?;;.C. and then 135.5 grams. of :BaO were added. :fIhe whole was heatedet .:.C.,. and SOD-grams of. a. :.1oW-yiscosity,. solvent-extracted :Mid-Conti- Jnent; oil were added. The temperature lWaS' then raised to 150 and CO2 was. blown through the .mass for about 2 hours. :35 gramsofi nonylalcoholwere added 1 and, the, mass. vwas :filtered to isolate. the desired .metal; complex :(the- .filtrate) which was a moderately viscous, :brown, oil-sol- ;uble, liquidhaving thefoll-owing. analysis:

Acid'No 30.5

Per cent sulphate ash '2 2.3

Metal ratio 3.72

'5'55 gramsof. a .40%,oil solution ,ofbarium petroleum sulphonate (10 sulphate ash content), 47 grams of ,diethyl maionate (ratio of equivalents of sulphonate to promoter is. 1.7), 91 gramsof a .lowrviscosity, solvent-extracted vMideContinent oil, and '70 grams of. water were-stirred together at 70C. and ,then 1355 grams. of BaO wereadded. The process was. then continued in thesame manner set forth inExample 10. Filtrationof "the process mass yielded the desiredmetal complex (the filtrate), which was .a free-flowing, brown, oil-solubleliquid .having the ,following analysis:

:Acid No 2102 Per cent sulphate ash 18.1

Metal ratio 2.46

EXAMPLE 21 Acid N0 0.3 Percent sulphate -ash 4 Metal ratio 1.05

Commonent A-- The oiksoluble organic acidQcompounds. used as starting, materials The organic acidcompound used as" one of th e tfloo -c nd -th =:5 grams fBa'O '75startingmaterials'inour processmay be the oil soluble organic acid itself and/or an alkaline earth metal salt thereof. At this point it should be noted that whereas Mertes found it necessary to first prepare a normal metal salt and then react such normal salt with an additional amount of a salt-forming material, our process can be carried on as a, one-step process by beginning with the oil-soluble organic acid. While it is possible to first prepare the normal metal salt of the organic acid in the usual way, by a conventional salt-forming procedure, and then begin our process by utilizing such normal metal salt as one of the starting materials, it may be more convenient to employ as the starting material the organic acid rather than the salt thereof. Our process is operable for the production of certain types of compounds when utilizing as starting materials any of the products produced by the prior art processes. Also, as a starting material, mixtures of acids and salts can be used to produce the complex. The variety of classes of organic acids which can be employed are, for example, sulphur acids, carboxylic acids, phosphorus acids, etc. of the aliphatic and cyclic types, and the corresponding thio-acids.

More specific examples of organic acids are the sulphur acids including sulphonic, sulphamic, sulphinic, thiosulphonic, etc., and of these the sulphonic acids will find particular application under the present invention. A more specific identification of the sulphonic acids is given hereinbelow.

The carboxylic acids include the fatty acids wherein there are present at least about 12 carbon atoms, such as, for example, palmitic, stearic, myristic, oleic, linoleic, etc. acids. The carboxylic acids of the aliphatic type can contain elements in the aliphatic radical other than carbon and hydrogen; examples of such acids are the carbamic acids, ricinoleic acids, chlorostearic acids, nitro-lauric acids, etc. In addition to the aliphatic carboxylic acids, it is intended to employ the cyclic types such as those containing a benzenoid structure, 1. e., benzene naphthalene, etc., and an oil-solubilizing radical or radicals having a total of at least about 15 to 18 carbon atoms. Such acids are the oil-soluble aliphatic substituted aromatic acids as for example, stearylbenzoic acids, monoor polywax substituted benzoic or naphthoic acids wherein the wax group contains at least about 18 carbon atoms, cetyl hydroxy-benzoic acids, etc. The cyclic type of carboxylic acids also includes those acids which have present in the compound a cycloaliphatic group. Examples of such acids are petroleum naphthenic acids, cetyl cyclohexane carboxylic acids, di-lauryl deca-hydronaphthalene carboxylic acids, di-octyl cyclopentane carboxylic acids, etc. It is also contemplated to employ the thio-carboxylic acids, that is, those carboyxlic acids in which one or both of the oxygen atoms of the carboyxlic group are replaced by sulphur. These carboxylic and thiocarboxylic acids can be represented by the following formulae:

wherein R is an aliphatic radical, a: is at least 1, and (R n contains a total of at least about 15 to 18 carbon atoms; T is a cyclic nucleus such as benzene, naphthalene, diphenyl ether, diphenylene oxide, diphenyl sulphide, diphenylene sulphide, phenol, hydroxy-naphthalenes, phenol disulphides, petroleum naphthenes, cyclohexane,

cyclopentane, chloro-cyclohexane, nitro-cyclopentane, deca-hydronaphthalene, mercaptodeca-hydro-naphthalene, etc.; and X is either oxygen or sulphur. In Formula 11, R is an aliphatic group containing at least 12 carbon atoms and X is either oxygen or sulphur. R, R, and T can also contain other substituent groups such as nitro, amino, hydroxy, mercapto, halogen etc. Representative examples are nitro-stearic acids, ceryl-chloro salicylic acids, chloro-palmitic acids, cetyl-anthranilic acids, stearyl-mercaptonaphthoic acids, etc.

The phosphorus acids include triand pentavalent organic phosphorous acids and the corresponding thio-acids, which are, for example, phosphorus, phosphoric, thiophosphoric, thiophosphorous, phosphinic, phosphonic, thiophosphinic, thiophosphonic, etc. acids. Among the most useful of the phosphorus acids are those represented by the following formulae:

wherein X and X are either oxygen or sulphur and at least one X and one X is sulphur, and R and R are each either the same or different organicradicals or hydrogen, and wherein at least one isan organic radical and at least one R is hydrogen and wherein at least one R is an organic radical and at least one R is hydrogen. Therefore, such formulae include the oil-soluble organic thio-acids of phosphorus, more particularly the organic thiophosphoric acids and the organic thiophosphorous acids. The organic radicals R and R can be aliphatic, cycloaliphatic, aromatic, aliphaticand cycloaliphatic-substituted aromatic, etc. The organic radicals R and R preferably contain a total of at least about 12 carbon atoms in each of the above thio-acid types I and II. Examples of such acids are dicapyryl dithiophosphoric acids, di-(methyl-cyclohexyl) dithiophosphoric acids, dilauryl dithiophosphoric acids, dicapryl dithiophosphorous acids, di-(methyl-cyclohexyl) dithiophosphorous acids, lauryl monothiophosphoric acids, di- (butyl-phenyl) dithiophosphoric acids, and mixtures of two or more of the foregoing acids.

Certain of the above described thio-acids of phosphorus such as for example di-capryl dithiophosphoric acid are also commonly referred to as acid esters.

As indicated, our process is applicable not only when using the oil-soluble organic acid as such as one of the starting materials, but also the alkaline earth metal salts of such organic acids. The present process will produce a high metal content organo metallic material when as one of the starting materials one uses any of the metal organic complexes produced by the prior art workers, such as for example, Bergstrom, Griesinger, Campbell et al., and Mertes. We thus may utilize as a starting material the end product produced by these prior art workers and from them produce the novel high metal content complex of our invention.

From the broad class of available organic acid compounds, it is preferred to employ the oilsoluble sulphonic acid compounds. Furthermore, of the available alkaline earth metal salts of organic acids, the barium salts thereof are preaerator ferred for'" the reason that unexpectedl exculent results are obtained by the use thereof. These oil-soluble sulphonic acids, and the alkaline earth metal salts thereof can be represented by the following structural formulae:

'radical containing a total of at least about '15 to 18 carbon atoms, and M is either an alkaline earth metal, preferably barium, or hydrogen. When R is an aliphatic substituted cycloaliphatic group, the aliphatic substituent should contain a total of at least about 12 carbon atoms. Examples of types of the R" radicalare alkyl, alkenyl, and alkoxy-alkyl radicals, and aliphatic substituted cycloaliphatic radicals where the aliphatic group is alkyl, alkoxy, alkoxy-alkyl, carboalkoxyalkyl, etc. Specific examples of R are cetyl-cyclohexyl, lauryl-cyelohexyl, ceryloxyethyl, and 'octadecenyl radicals, and radicals derived from petrolatum, saturated and unsaturated parafiin wax, poly olefins, including poly-C3, C4, C5, C6, C1, C8, olefin hydrocarbons. The groups T, R and R in the above formulae can also contain other organic or inorganic substituents in addition to those enumerated above, such as for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, carboxy, ester, etc.

In Formula I above, :11, y, z and b are at least one; whereas in Formula II a, d, and c are at least one.

The following are specific examples of oil-soluble sulphonic acids coming within Formulae I and II above, and it is to be understood that such examples serve to also illustrate the alkaline earth metal salts of the sulphonic acids. In other words, for every sulphonic acid, it is intended that the alkaline earth metal salt thereof is also illustrated. This includes specifically, the barium, strontium, calcium and magnesium salts of the hereinbelow illustrated sulphonic acids.

Such sulphonic acids are mahogany sulphonic acids; petrolatum sulphonic acids; monoand polyvvax substituted naphthalene sulphonic, phenol sulphonic, diphenyl ether sulphonic, diphenyl ether disulphonic, naphthalene disulphide sulphonic, naphthalene disulphide disulphonic, diphenyl amine disulphonic, diphenyl amine sulphonic, thiophene sulphonic, alphachloronaphthalene sulphonic acids, etc.; other substituted sulphonic acids such as cetyl chlorobenzene sulphonic acids, cetyl-phenol sulphonic acids, cetyl-phenol disulphide sulphonic acids, cetyl-phenol mono-sulphide sulphonic acids, cetoxy capryl-benzene sulphonic acids, di-oetyl thianthrene sulphonic acids, di-lauryl betanaphthol sulphonic acids, and di-capryl nitronaphthalene sulphonic acids; aliphatic sulphonic acids such as paraffin Wax sulphonic acids,'un-

saturated parafiin wax sulphonic acids, hydroxy V substituted parafiln wax-sulphonic acids, tetrais'obutylene sulphonic acids, tetra-amylene suiphonic acids, chloro-substituted paraflin W'ax tended herein to employ the term petroleum sulphonic acids to cover all sulphonic acids which are derived from petroleum products. Additional examples of sulphonic acids and/or alkaline earth metal salts thereof which canbe employed as starting materials are disclosed in the following U; S. patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791; 2,212,- 786; 2,213,360; 2,228 598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,- 121; 2,321,022; 2333,558; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,383,319.

Of the various types of organic acids and alkaline earth metal salts thereof enumerated above, i. e. sulphur acids, carboxylic acids, phosphorus acids, etc., it is preferred to employ the sulphurbearing organic acids or alkaline earth metal salts thereof. However, it is to be understood that all of organic acids and salts thereof are not equivalent in their ability to complex with unusual amounts of inorganic alkaline earth metal compounds in the presence of a promoter, because under certain conditions, some organic acids or salts thereof are more effective than others.

Component B-The promoter material The promoters employed in the process ofthis invention are enolic organic compounds having an ionization constant greater than 1 l0- at 25 C., water solubilities of at least about 0.0005% at 50 C., and saturated aqueous solutions of which at about 25 C. exhibit a pH not greater than 7.

The term enolic organic compounds as used in the specification and appended claims refersto tautomeric organic compounds of the established type, for example, as illustrated in Advanced Organic Chemistry, by G. W. Wheland, John Wiley El Sons, New York, 1949, chapt. 14, pp. 580 to 646.

Generally, the enolic organic compounds include a variety of classes of compounds such as aliphatic nitro compounds (i. e. aci-nitro compounds), oximes, imines, imides, amides, ketoesters, polyesters, and polyketones. It will be noted that the term enolic carbonyl includes keto-esters, polyesters, and polyketones.

The aliphatic nitro compounds (aci-nitro compounds) useful as promoters include, for example, 1 (para-nitrophenyl) 2 nitrobutane; gammanitro methyl hexoate, l-chloro Lilitrdprop'ane, l-nitropropane, etc.

The oximes useful as promoters include, for example, benzalacetone oxime, lquinone monooxime, isophorone oxime, etc.

The amides useful as promoters-include, for

example, N-e'thyl benzamide, ortho-chlorobenzamide, benzamide, acetanilide, thiodiglycolic acid diamide, acetamide, etc.

The enolic carbonyl compounds useful as promoters include, for example: keto-esters, such as,

phenyl acetoacetate, ethyl acetoacetate, benzyl 'aeetoacetate, chloro naphthol 'acetoacetater" etc.

2,374,193 and polyesters, such as, dibenzyl malonate, diethyl malonate, triethylcarballyate, etc.; and polyketones, such as, benzoyl acetone, acetyl acetone, etc.

Component C-The alkaline earth metal saltforming compounds The salt forming compounds which are employed to impart to the process mass the specified amount of metal may be broadly defined as inorganic alkaline earth metal compounds wherein anionic radicals may be, for example, hydroxyl, oxide, carbonate, bi-carbonate, sulphide, hydrosulphide, halide, hydride, amide, basic carbonate, etc. Of the inorganic alkaline earth metal compounds, good results are obtained with those having a water solubility of at least about 0.0003% at 50 C., and preferably at least about 0.006%. Still more preferred are those inorganic alkaline earth metal compounds, saturated aqueous solutions of which give an alkaline reaction or pH value greater than '7.

To further illustrate the large number and variety of classes of inorganic compounds which can be employed, specific examples thereof are enumerated below.

The alkaline earth metal inorganic compounds include the barium containing compounds such as barium hydroxide, barium oxide, barium sulfide, barium carbonate, barium bi-carbonate, barium hydride, barium amide, barium chloride, barium bromide, barium nitrate, barium sulfate, barium borate, etc.; the calcium containing compounds such as calcium hydroxide, calcium oxide, calcium sulfide, calcium carbonate, calcium bicarbonate, calcium hydride, calcium amide, calcium chloride, calcium bromide, calcium nitrate, calcium borate, etc.; the strontium-containing compounds such as strontium hydroxide, strontium oxide, strontium sulfide, strontium carbonate, strontium bicarbonate, strontium amide, strontium nitrate, strontium hydride, strontium nitrite, etc.; the magnesium-containing compounds such as magnesium hydroxide, magnesium oxide,

magnesium carbonate, magnesium bicarbonate,

magnesium nitrate, magnesium nitrite, magnesium amide, magnesium chloride, magnesium sulfate, magnesium hydrosulfide, etc. The corresponding basic salts of the above described compounds are also intended, however, it should be understood that the inorganic alkaline earth metal compounds are not equivalent for the purposes of the present invention, because under certain conditions some are more effective or desirable than others.

The acidic material As previously indicated, one form of the process of the present invention includes the step of treating the immediate complex product with an acidic material for the purpose of liberating therefrom at least a portion of the material previously referred to as the promoter. A particu- .the effect of freeing from the immediate complex product formed at least a portion'of the pro- ,moter used. Thus the presence in the immediate complex product of the promoter material, in combined form, clearly distinguishes the immediate complex product from any metal organic complex type material heretofore produced. Moreover, the nature of the product formed by regenerating from the immediate end product at least a portion of the promoter material leaves that complex with a composition which is quite difierent from the other prior art metal organic complexes previously produced. It is recognized that in accordance with the present invention, the alkaline earth metal salt of the ionizable organic compound can be employed as the promoter in forming the salt complex, however, when such a salt is used as the promoter and the resulting complex is treated with an acidic material, the metal-free ionizable organic compound is freed from its salt.

For the purpose of releasing the ionizable organic compound used as a promoter from the complex, an important feature or characteristic of the acidic material is that it must, when present in the mass containing the complex, possess an ionization constant higher than the ionizable organic compound used as the promoter. Thus, for the purpose of this specification and the appended claims, it is to be understood that the acidic material can be either a liquid, gas, or solid, prior to being incorporated in the mass which contains the salt complex.

The acidic material usually employed is a liquid or a gas. The liquids can include the strong or weak acids, such as, for example, hydrochloric,

sulphuric, nitric, carbonic acids, etc., whereas the gas is for the most part an anhydride of an acid or an acid anhydride gas.

The following are additional specific examples of acidic materials, viz.: HCl, S02, S03, C02, air (considered acidic because of C02 content), N02, H2S, N203, PCls, S0012, C102, H2Se, BF's, CS2, COS, etc.

It is to be understood, however, that all acidic materials are not equivalent for the purposes of the present invention, but that under certain conditions, some are more effective or desirable thanothers.

The complex of the present invention can be produced by using the same alkaline earth metal in the organic acid compound, promoter and inorganic compound; or such complexes can be derived from components containing dissimilar alkaline earth metals. In some instances it is desirable to employ a mixtureof organic acid compounds which contain at least two or up to and including four dissimilar alkaline earth metals; or the same distribution of metals can be obtained by varying the type of promoter and/or inorganic compound in various combinations with the organic acid compound. It is therefore possible to employ various combinations of dissimilar alkaline earth metals in the starting materials used in preparing the complex product.

Process conditions The salt complex of the present invention is prepared by combining the aforementioned compounds in the presence of water. The water can be present as a result of addition thereof to the mixture, or liberated from either the essential components or other additionally present compounds as a result of being subjected to heat. However,-1t is preferred to add water to the mixture to effect salt complex formation. It has been found that the metal complex can be prepared when using small quantities of water such asabout 1 molecf water per mole of inorganic metal compound. However, more usually about 5 to 50, and preferably about to 30, moles of water per mole of inorganic metal compound are used.

Generally the complex formed with the inorganic alkaline earth metal compound, the oilsoluble organic acid or the alkaline earth metal salt thereof, and the promoter is prepared by heating the components in the presence of water at a superatmospheric temperature while'in'suring thorough mixing andthen still further heating said mixture to substantially remove all of the water. Atleast five methods are available by which the complex can be formed, namely:

, (a) The promoter is added to the oil-soluble normal salt of the organic acid, followed by addition of an aqueous solution. or suspension of the inorganic alkaline earth metal compound thereto; the mixture is held at a superatmospheric temperature for a reasonable length of time while effecting thorough mixing, and then the total mixture is further heated to remove substantially all water which might be present;

(2)) The inorganic alkaline earth metal compound in a dry state is added to a mixture of organic acid or a normal salt of such organic acid,, promoter and water heating while insuring thorough mixing, and then further heating to remove substantially all of the water;

(0) The acid of the desired salt of organic acid is mixed with the promoter, then an aqueous solution or suspension of the inorganic alkaline earth metal compound is added thereto, the mixture is heated and agitated at a superatmospheric temperature for 'a time sufficient to insure thorough mixing, and followed by subjecting the total mixture to dehydration conditions in order to'remove substantially all of thewater;

(d) In any of the methods discussed herein for preparing the salt complex, a substantial increase in metal content is usually effected by treating'the mass containing the complex product with an acidic material just after substantial amounts of water are driven off and just before the mass is filtered.

(e) The sediment formed from any of the aforementioned methods can be employed either alone or with additional promoter in any of the three methods given above.

In all of the methods described above for preparing the salt complex, the step of removing substantially all ofthe water which is present is accomplished at a temperature not substantially in excess of 350 C, preferably about 110 C. to 200 C. The technique employed to remove the'wa'ter includes, for example, a conventional flash fstripping operation which involves pass-- ing the material in a thin film state over a large to remove the last portion? of water. It can "therefore be seen that the temperature as well as the time for effecting substantial removal! of water will vary considerably: depending on the amount of material being.- processedand on the technique, employed therefon Generally, the

time required to efiect substantial removal of water isat least about 15 minutes .or less and can be as high as 10-15 hours or more. 1 Usually,

however, it is most convenient to employ atmospheric pressure for such an operation, and consequently it requires about 1 to 5 hours to remove substantially all of the water from the process mixture; It was observed that satisfactory complexes are obtained when using any of the techniques described above, and that the final water content can be up to about 2% or more.

'Usually, as indicated above, the components are combined and agitated at an elevated temperature to insure thorough mixing, and then water is removed therefrom. It should be under? stood that the process to form the complex can be effected without the preliminary heating and mixing period, if desired. It is therefore not essential to this invention to have such apreliminary step because all that appears necessary is to mix the components and remove substantially any water which is present.

For the purposes of this specification and the appended claims, the relative amounts of oilsoluble organic acidor the alkaline earth metal salt thereof and promoter is expressed in the ratio of equivalents of the former to the latter. In accordance therewith, the ratio of equivalents of oil-soluble organic acid or the alkaline earth metal salt thereof to promoter is from about 1 to 10 to about 10 to 1, more usually from about 1 to 1 to about 10 to l, and preferably from about 3 to 2.to about'7to 2. I

The amount of inorganic alkaline earth metal compound employed generally will be sufficient to have present in the total mass at least more than about one equivalent of alkaline earth metal, regardless of how combined, per equivalent of oil-soluble organic acid or the alkaline earth metal salt thereof plus promoter. In other words, the amount of inorganic alkaline earth metal compound employed must be such that there is more than the theoretical amount required to form merely a normal salt of the oilsoluble organic acid and the promoter. Thus, for the purposes of this specification and the appended claims, the amount of inorganic alkaline earth metal compound employed will be expressed as an amount such that thereare present in the mass more than one equivalent of alkaline earth metal, including the alkaline earth metal which is present in the form of the salt of the oil-soluble organic acid and thepromoter, per equivalent :ofpil-soluble organic acid and alkaline earth metal salt thereof plusthe promoter.

As indicated hereinabove, treatment of the salt complex with an acidic material-is done in instances where it is desirableto lower the'basic number oflthesalt complex and/ or'par-tially or substantially completely recover the ioni-zable organic compound. This treatment is effected at a temperature of from about 25 to 250 C., preferably from about 50 to 1'70 C. and usually employing from about 0.5 to 20% of acidic material, based on. the weight of salt complex. The time of treatment with the acidic material can vary considerably depending on the desired result. As would be expected, short periods or" treatment may cause only partial liberation or release of ionizable organiccompound or small decreases in the-basic number of the salt complex. However, in general, periods of treatment will range from about 0.25 to 30 hours or more. In most cases, and particularly where it is desired to recover the promoter, the amount of acidic material used should be at least equivalent to the .izable form of: promoter.

When it is desired to roduce a product having substantially neutral reaction, the amount of acidic material used should be at least equivalent to the total metal in excess of that present as the normal salt of the oil soluble organic acid.

To substantially increase the metal content of the salt complex, it may be desirable to treat the total mass with an acidic material just prior to filtering same. This treatment may conveniently be eife'cted at a temperature of from about to 250 C. preferably from about 50 to 170 C., using from about 0.5 to 20 of acidic material, based on the total mass, and for a period of from about 0.25 to hours. The acidic material employed is preferably an acid anhy-dride gas, as defined hereinabove. Treatment with the acid anhydride gas may be accelerated by superatmospheric pressure.

As indicated above, in order to facilitate an understanding of the amount of metal which can be present in the salt complex, the metal ratio is defined as the ratio of the total metal in the salt complex to the amount of metal which is in the form of a normal salt of the oil-soluble organic acid. In accordance therewith, the salt complex as of this invention will have metal ratios greater than 1 and up to 10 or more, preferably from about 2 to 8. As for the finished salt complex which is treated with an acidic material, the metal content is substantially the same as i the complex prior to treating. Consequently the same metal ratios as given above will apply to such treated product. In those instances where the finished salt complex is treated with an acidic material and the ionizable organic compound is removed from the resultant product by distillation, or otherwise it is found that the metal ratios will be substantially the same as in the salt complex before treating with the acidic material.

By reason of the high metal ratio of the complexes produced in accordance with this invention, the following theories are suggested as a possible explanation of how the metal is combined. It is to be understood, however, that such theories are advanced for the purpose of offering explanations, and are not to be construed as limitations on the scope of the present invention.

In the following equations, AXH represents a promoter in which H is an ionizable hydrogen and M represents a divalent metal. Assuming that the promoter may act as a catalyzer for the formation of inorganic ploymeric configurations, viz. (M-O) XH, which are bonded to the acid group (e. g., the 'sulphonate radical in the preferred instance), the possible reactions that may occur with the sulphonate radical are:

(1) 2RSO3H M(OH)2 (RSO3)2M ZHzO 2AXHM(OH) o (AXhM (peptlzed into end product).

The resultant complex, according to the above theory, can be a complex mixture of all the po- 20 tential products listed above. It is apparent that high metal ratios are possible under this theory.

Another theory is based upon an electronic interpretation. For example, in the case of the neutral sulphonate, the charges are distributed as follows:

The electron octets around the two oxygen atoms which are not attached to a metal atom give to each of these atoms a unit negative charge, thus leaving the sulphur atom with a double positive charge.

When the sulphonate, excess inorganic metal com-pound, promoter, and water are reacted according to the present invention, a basic promoter salt. AXMOH is presumed to be formed. This normally oil-insoluble salt dissolves in the reaction mixture because of the electronic attracting force known as a hydrogen bonding. structurally this can be shown as:

Structure (a) would have a metal ratio of 3.0, and structure (b) would have a metal ratio of 5.0. Combinations of neutral sulphonate and one or both structures would explain the whole number and fractions of metal ratios which are obtained in actual practice.

After the structures (a) and (b) are formed, if hydroxyl ions are present in the reaction mass the following reactions may take place:

Structure ((1) on- R(S|++)-OM AX- (|)"...H...OMOH Structure ((2) 2011- R(S++)OM 2AX' o...H... 0MOH The AX ions may then react with M(OH)2 to produce more AXMOH, and the latter would in turn lead to the formation of additional amounts of structures (a) and (b). The cycle may occur repeatedly.

According to this electrode explanation, the AX residue of the basic promoter salt appears to function as a carrier for the M(OH)2, and thus facilitating the communicating of the M(OH)2 into close positions with the negatively charged oxygen atoms of the sulphonate radica.

Having thus described the present invention by furnishing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be imposed by reason thereof, but that the scope of this invention is defined by the appended claims.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmissions, gears, etc. as well as in torque converter oils. Other suitable uses for such complexes are in asphalt emulsions, insecticidal compositions, fire- .proofing and stabilizing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal-drawing compositions, flushingoils, textile. treatment compositions, tanning a'ssistants, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetrating agents, gum solvent compositions, fat splitting agents, bonding agent for ceramics and. asbestos, asphalt improving agents, flotation agents, improving agents for hydrocarbon fuels such as e. 'g., gasoline and fuel oil, etc.

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, particularly the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred Range Range 7 Range Percent Percentv Percent Lubricant 0. (ll--20 0. 2-l5 0. -10 Stabilizing Agent for Plastics 0.05- 5 0.1- 3' 0.2- 2 Paint Drier 0. 225 0. 5-20 1. 0-15 To better appreciate the wide variety of uses to which the salt complexes of this invention are adapted, ,the following specific examples are iven:

Uses in lubricants: Percent by weight SAE 20 motor oil 94.0 Product of Example 3 6.0

SAE 30 motor oil 96.5 Product of Example 4 2.5 Barium di-lauryl dithiophosphata--- 1.0

SAE 30 motor oil 95.5

SAE 30 motor oil 94.0 Product of Example 5.0 P2S5 treated turpentine 1.0

SAE motor oil 95.0

Product of Example 3 4.0 Pass-treated turpentine 0.5 Zinc di-n-hexyl dithiophosphate 0.5

Use as a stabilizing agent for halogen-bearing plastics:

Poly-chloroprene 40.0 Di-lauryl sebacate 59.25 Product of Example 12 075 Use as a paint drier:

Enamel (alkyd resin) 98.5 Product of Example 3 1.5

Other modes of applying the principle'of, the inventionmaybe employed, change being made as regards the details described, provided the features stated in any of the following claims, or theequivalent of such, be employed.

We therefore particularly point out andqdistinctly claim asour invention:

1. A process which comprises preparing-. and mixing a mass in which, at 50 0., at least 50% of, the components are in the liquid state, .and in which mass the active components consist of:

A; An oil-soluble organic acid compoundconta'ining at least 12 carbon atoms in the molecule selected from the class consisting of the'aliphaticand cyclic; sulphur acids, carboxylic acids, phosphorus acids, the thio acids corresponding to any of the foregoing acids, and the alkaline earth metal salts of any of-said acids: r i 1 B. An organiccompound selected from theclass consisting of enolic organic compounds and the alkaline earth metal salts thereof, said enolic organic compoundshaving (1) An ionization constant in water of at least about 1X10- at about 25 C;;

(2) 'A water solubility at 50 C. of at" least about .0.0005%; and (3) In saturated aqueous solutions at about 25 C. a pH of less than 7;

the relative amounts of A and B used being in the rangeof from about one equivalent of-A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B;

C. An inorganic alkaline earth metal compound;

(1) Which is water-soluble at a temperature of 50 C. to the extent of at least about 0.0003%;

(2) In an amount such that there are present in the mass substantially more than 1 equivalent of alkaline earth metal, including the alkaline earth metal present in the remaining components, per equivalent of A plus B; and

D. Water, in an amount equal to at least about one mole per mole of C;

maintaining the mass at a temperature and for a period of time sufiicient to drive off substantially all free water and water of hydration which may be present, and form the organic alkaline earth metal complex; and then treating the organic alkaline earth metal complex with an acidic material of which the ionization constant is higher than the ionization constant of the organic salt-forming compound of com-' ponent B and in amounts sufficient to liberate a substantial proportion of said organic compound of component B.

2. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are enolic aliphatic nitro compounds of the type in which the nitro group is attached to a non-tertiary carbon atom in an aliphatic group. 7

3. A process in accordance with claim 1 further characterized in that the enolic organic compounds of components B are enolic nitro paraflin hydrocarbons or the type in which the nitro group is attached to a non-tertiary carbon atom in an aliphatic group.

4. A process in accordance with claim 1 further characterized in that the enolic organic compound of component B is l-nitro-propane.

5. A process in accordance with claim 1 fur- 23 ther characterized in that the enolic organic compounds of component B are oximes.

6. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are cycle-aliphatic oximes. '1

7. A process in accordance with claim 1 further characterized in that the enolic organic compound of component B is isophorone oxime.

8. A process in accordance with claim 1 further characterized in that the enolic organic compound of component B is 4-keto-2-pentylidene imine.

9. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are amides.

10. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are aromatic amides.

11. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are non-metal inorganic substituted aromatic amides.

12. A process in accordance with claim 1 further characterized in that the enolic organic compound of component B is ortho-chloro benzamide. V

13. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are carbonyl compounds.

14. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are polyketones.

15. A process in accordance with claim 1 further characterized in that the enolic organic compounds of component B are aliphatic polyketones.

16. A process in accordance with claim 1 further characterized in that the enolic organic compound of component B is acetyl acetone.

17. As a new composition of matter, an oilsoluble reaction product produced by the process of claim 1, which is substantially free of a salt of said low molecular weight organic compound of component B.

18. As a new composition, the oil-soluble reaction product mass produced by the process of claim 1, which includes as a component thereof a substantial proportion of the metal-free, low molecular weight organic salt-forming compound of component B liberated from said organic alkaline-earth metal complex.

PETER A. ASSEFF." THOMAS W. MASTIN. ALAN RHODES.

REFERENCES CITED The following references are of record in the file of this patent:

Wheland, Adv. Org. Chem., 2nd. Ed. (1949) pp. 580-646. 

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: A. AN OIL-SOLUBLE ORGANIC ACID COMPOUND CONTAINING AT LEAST 12 CARBON ATOMS IN THE MOLECULE SELECTED FROM THE CLASS CONSISTING OF THE ALIPHATIC AND CYCLIC; SULPHUR ACIDS, CARBOXYLIC ACIDS, PHOSPHORUS ACIDS, THE THIO ACIDS CORRESPONDING TO ANY OF THE FOREGOING ACIDS, AND THE ALKALINE EARTH METAL SALTS OF ANY OF SAID ACIDS; B. AN ORGANIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF ENOLIC ORGANIC COMPOUNDS AND THE ALKALINE EARTH METAL SALTS THEREOF, SAID ENOLIC ORGANIC COMPOUNDS HAVING (1) AN IONIZATION CONSTANT IN WATER OF AT LEAST ABOUT 1X10-10 AT ABOUT 25* C.; (2) A WATER SOLUBILITY AT 50* C. OF AT LEAST ABOUT 0.0005%; AND (3) IN SATURATED AQUEOUS SOLUTIONS AT ABOUT 25* C. A PH OF LESS THAN 7; THE RELATIVE AMOUNTS OF A AND B USED BEING IN THE RANGE OF FROM ABOUT ONE EQUIVALENT OF A TO ABOUT 10 EQUIVALENTS OF B OF ABOUT 10 EQUIVALENTS OF A TO ABOUT ONE EQUIVALENT OF B; C. AN INORGANIC ALKALINE EARTH METAL COMPOUND: (1) WHICH IS WATER-SOLUBLE AT A TEMPERATURE OF 50* C. TO THE EXTENT OF AT LEAST ABOUT 0.0003%; (2) IN AN AMOUNT SUCH THAT THERE ARE PRESENT IN THE MASS SUBSTANTIALLY MORE THAN 1 EQUIVALENT OF ALKALINE EARTH METAL, INCLUDING THE ALKALINE EARTH METAL PRESENT IN THE REMAINING COMPONENTS, PER EQUIVALENT OF A PLUS B; AND D. WATER IN AN AMOUNT EQUAL TO AT LEAST ABOUT ONE MOLE PER MOLE OF C; MAINTAINING THE MASS AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREE WATER AND WATER OF HYDRATION WHICH MAY BE PRESENT, AND FORM THE ORGANIC ALKALINE EARTH METAL COMPLEX: AND THEN TREATING THE ORGANIC ALKALINE EARTH METAL COMPLEX WITH AN ACIDIC MATERIAL OF WHICH THE IONIZATION CONSTANT IS HIGHER THEN THE IONIZATION CONSTANT OF THE ORGANIC SALT-FORMING COMPOUND OF COMPONENT B AND IN AMOUNTS SUFFICIENT TO LIBERATE A SUBSTANTIAL PROPORTION OF SAID ORGANIC COMPOUND OF COMPONENT B. 